Pad dyeing



Patented July 18, 1950 PAD DYEING Norman S. Cassel, Ridgewood, andAlfred '1'.

Clifford, Fair Lawn, N. .L, assignors to Interchemical Corporation,New'York, N. Y., a cornotation of Ohio No Drawing. Application January27, 1947,

- Serial No. 724,704

Claims. 1

This invention relates to the dyeing of textiles and is particularlyconcerned with the use in the dyeing of fabrics and textile materials ofa composition comprising a dispersion of a. water-insoluble pigment inan aqueous solution containing a water-soluble heat-precipitable alkylcellulose, a water-soluble thermosetting resin, and a hydrophilicglycoside which may be either a water-soluble nonheat-precipitablecellulose ether or a mannogalactan flour.

In our copending application, Serial No. 627,798, filed November 9,1945, of which the present application is a continuation-in-part, wehave disclosed the use in the pad-dyeing of textiles of a dye bathcomprising a pigmented aqueous solution of a water-solubleheat-precipitable alkyl cellulose such as methyl cellulose, and awatersoluble thermosetting resin. The use of this paddyeing compositioninvolves simply applying the pigmented dye bath to the fabric to bedyed, heating the fabric to a temperature just sufiicient to precipitateor gel the alkyl cellulose, and thereafter further heating the fabric todry it and to insolubilize the resin. By reason of the precipitation orgelation of the alkyl cellulose during the initial heating to which thefabric is subjected, excellent control and efiective prevention ofmigration and flocculation of the pigment during the subsequent heatingof the fabric to vaporize the water and to set the resin are obtained;and a level, even dyeing and a uniform, good color value are produced inthe finished fabric.

The utilization of this heat-precipitable alkyl cellulose system hasbeen found to involve certain diificulties under some operatingconditions, however. As pointed out in our copending application, thedye bath should contain a sufficient amount of water-solubleheat-precipitable alkyl cellulose so that migration and flocculation ofthe pigment on drying can be satisfactorily controlled; and relativelylarge amounts are usually required for this purpose. cellulose, forexample, the concentration preferably ranges from about 1 to 3% byweight; although lower concentrations can be used, in general from 0.25to 0.5% by weight is the lowest amount that is practicable.

Special heating techniques are necessary to effect the precipitation orgelation of the alkyl cellulose, which should be precipitated or gelledbefore any substantial or appreciable vaporization of the water takesplace. Except in the case in which a water-soluble salt such as asulfate, tartrate or phosphate is added to the dye bath to lower theprecipitation or gelation temperature of the alkyl cellulose, the paddedfabric cannot be satisfactorily dried by passage over the customarysteam-heated drying cans or through a low-temperature drying oven.Moreover, with a decrease in the concentration of the alkyl cel- In thecase of methyl,

2 lulose, difficulty is encountered in obtaining satisfactory control ofthe migration and flocculation of the pigment on drying unless undueprecautions are taken in the precipitation of the alkyl cellulose.

Relatively severe curing conditions are required for insolubilization ofthe thermosetting resin. Generally, it is necessary to subject the driedfabric to a temperature of at least 350 to 400 F. for a period of 2 to 3minutes to obtain satisfactory fastness to washing. The padded fabric,moreover, cannot be printed with a vat or an azo color prior to theresin-curing stage because it is not rendered sufficiently wash-fast ondrying to withstand the required acid or steam-aging.

We have now discovered that these difficulties can be largely eliminatedor substantially alleviated by incorporation of a hydrophilic glycoside,which may be either a water-soluble nonheatprecipitable cellulose etheror a mannogalactan flour, in such a pigmented aqueous dye bath. Theinclusion of such a hydrophilic glycoside in this dye bath permitssatisfactory control of migration and flocculation of the pigment ondrying to be obtained with concentrations of the heat-precipitable alkylcellulose considerably less than that which would otherwise benecessary. Careful heating of the wet dyed fabric to effectprecipitation or gelation of the alkyl cellulose prior to anyappreciable vaporization of the water is no longer essential, andefiective prevention of pigment migration and flocculation is obtainedby passage of the padded fabric directly over steamheated drying cans orthrough a low-temperature drying oven. Much less severe conditions 'arerequired to insolubilize the resin and passage of the fabric oversteam-heated drying cans or through a low-temperaturedrying ovenaccomplishes sat isfactory curing of the resin. Moreover, the fabric isrendered sufficiently wash-fast by passage over such drying cans orthrough such a drying oven so that it can be printed with a vat or anazo color and subjected to the required acid or steam-aging treatmentprior to curing of the resin. A crisp finish can also be imparted to thedyed fabric without subjection thereof to the customary starchtreatment.

The present composition comprises a dispersion of a water-insolublepigment in an aqueous solution of a Water-soluble heat-precipitablealkyl cellulose, a water-soluble thermosetting resin, and a hydrophilicglycoside which may comprise either a water-soluble nonheat-precipitablecellulose ether or a mannogalactan flour. Advantageously, thenonheat-precipitabl'e cellulose ether comprises a water-solublehydroxyalkyl cellulose ether, preferably hydroxyethyl cellulose ether;and the mannogalactan flour comprises a vegetable gum such as guar flouror locust bean gum. Preferably, the heat-precipitable alkyl cellulosecomprises a water-soluble lower alkyl cellulose such as methylcellulose.

As is the case with the pad-dyeing composition described in ourcopending application, any pigment can be incorporated into the presentcomposition provided it is sufliciently light-fast, does not bleed toany substantial extent in dry-cleaning .solvents such as naphtha andcarbon tetrachloride, and is sumciently resistant to soap. Suitablepigments include the phthalocyanines, various metal oxides, carbonblack, water-insoluble vat and azo dyestufis, and the like. Theparticular pigment selected for a given dyeing operation will depend notonly on its dispersibility and on the required color of course, but alsoon the nature of the finished goods.

Similarly, any water-soluble thermosetting resin can be employed in thepreparation of the present pigmented composition provided that theresulting heat-converted resin is sufficiently resistant to washing andis substantially insoluble in dry-cleaning solvents and provided that nothermosetting melamine-formaldehyde resins and water-solublethermosetting modified melamine-formaldehyde resins, particularlywatersoluble polyhydric alcohol-modified melamineformaldehyderesin's,and water-soluble thermosetting mixed urea-melamine-aldehyde resinsincluding water-soluble thermosetting urea-melamine-formaldehyde resinsand water-soluble thermosetting modified urea-melamine-formaldehyderesins, particularly water-soluble polyhydric alcohol-modifiedurea-melamine-formaldehyde resins.

Other water-soluble heat-setting resins, meeting the above requirements,such as water-soluble thermosetting phenol-formaldehyde resins andpolyvinyl alcohol-aldehyde resins can also he used, however. As with thepigment, the choice of the particular water-soluble heat-setting resinemployed will be governed to a large extent by the nature of thefinished fabric. Moreover, in some cases the reactants from which thewatersoluble resin is derived may themselves be incorporated in thecomposition and the resin subsequently formed therefrom.

As explained in our copending application, the alkyl cellulose utilizedin the present composition must be water-soluble and'must possess thefurther property of being soluble in water at low, ordinary roomtemperatures but insoluble in water at temperatures much above roomtemperature. As is well known, an aqueous solution oi such awater-soluble alkyl cellulose, upon being heated to a few degrees aboveroom temperature.

I forms a precipitate. Depending on the concentration of the particularalkyl cellulose, this precipi'tate appears either as a finely dispersedsolid or as a gel, the former resulting on the heating of very diluteaqueous solutions and the latter on the heating of more concentratedsolutions. In either event, on lowering of the temperature, theprecipitated alkyl cellulose redissolves, the formation of theprecipitate being reversible. (Unless otherwise specified, the termprecipitate, as used hereinafter in this specification, includes theterm "gel.)

The particular temperature at which precipitation or gelation of theaqueous solution of such a heat-precipitable alkyl cellulose takes placeis dependent not only on the particular alkyl cellulose employed butalso on the concentration of the alkyl cellulose solution and on theviscosity type of the alkyl cellulose. In general, there is a lowerlimit of concentration for an aqueous solution of a given alkylcellulose of a given viscosity type below which no appreciable gelationtakes place on heating, the precipitate in such case appearing as. afinely dispersed solid. As will become apparent hereinafter, however;the concentration of the heat-precipitable alkyl cellulose in thepresent composition advantageously falls within the range in whichprecipitation rather than gelation occurs.

Any of the water-soluble alkyl celluloses whose water solutions possessthe property of precipitating on heating, particularly the.water-soluble heat-precipitable lower alkyl celluloses, may be employedin the present composition. We have had particular success with thewater-soluble heat-precipitable methyl and ethyl celluloses,- especiallymethyl cellulose. Water-soluble heatprecipitable methyl cellulosecontains approximately between 1.3 and 2.6 methyl groups per glucoseunit, and the corresponding ethyl cellulose contains about 0.8 to 1.3ethyl groups per glucose unit. The raw material from which a given alkylcellulose is derived and the manner in which it is prepared exert, as iswell known, some influence on the water-solubility and theheat-precipitability of such alkyl cellulose. As already indicated,however, the particular alkyl cellulose employed must be bothwater-soluble and heat-precipitable.

The hydrophilic glycoside incorporated in the present compositioncomprises a water-soluble nonheat-precipitable cellulose ether or amannogalactan flour. Such cellulose ether, unlike the heat-precipitablealkyl cellulose, however, must be soluble in water both at roomtemperature and at elevated temperature, 1. e., its aqueous solutionshould not form a precipitate upon being heated above room temperature.Any cellulose ether that is both water-soluble and nonheat-precipitable,particularly the water-soluble nonheatprecipitable hydroxyalkylcellulose ethers such as hydroxyethyl cellulose ether, can be employedin the present composition. Especially satisfactory results have beenobtained with water-soluble nonheat-precipitable hydroxyethyl celluloseether. Other water-soluble nonheat-precipitable cellulose ethers such aswater-soluble nonheatprecipitable methyl cellulose, ether andwatersoluble nonheat-precipitable carboxymethyl cellulose ether can alsobe used, however.

The mannogalactan flour can conveniently be -y derived from a naturalsource and advantageously comprises a vegetable gum or flour, the chiefconstituent of which is the polysaccharide manno-' galactan. Thispolysaccharide is a high molecular weight carbohydrate which, onhydrolysis, yields mannose and galactose. Typical examples of such aflour include guar flour and locust bean (carob) gum. Only thosevegetable gums or flours of which the polysaccharide comprises the majororchief constituents are satisfactory for the present purpose, however.Other vegetable gums or flours, even though containing a small amountof. mannogalactan, such as ordinary starch, gum karaya, gum-tragacanth,and sodium alginate donot yield the present resultsrr In the preparationof the present composition, the water-soluble heat-precipitable alkylcellulose, the water-soluble thermosetting resin, aresinificationcatalyst if one is to'be included in the final composition, and thehydrophilic glycoside are dissolved in water in thedesired'concentrations- The resulting solution is then diluted withfurther waterif necessary, and an aqueous paste or dispersion of thepigment is stirred into the resulting mixture to provide the desired dyebath. The pigment may be prepared in paste form by mixing a precipitateof the pigment, e. g., a press cake thereof, and a suitable dispersingagent with sufficient water to form a paste of the de-' siredconsistency and'then grinding the mixture until the pigment is in afinely divided condition; or the pigment may be otherwise prepared in areadily dispersible form.

The several ingredients may, however, be admixed in any other suitablemanner, care being taken that the pigment is properly dispersed in thefinal composition. For example, separate solutions of one or more of thewater-soluble heat-precipitable alkyl cellulose, the'- watersolublethermosetting resin, and the hydrophilic glycoside may be prepared; andsuch solutions and the pigment dispersion may be admixed in anyappropriate'order.

Our pigment-dyeing composition can be readily applied to a fabric bymeans of a pad-dyeing operation, the fabric to be dyed being immersedtherein and then passed through the customary rollers for removal of theexcess dyeing composition. The dyed fabric is then subjected to heat inorder to precipitate the heat-precipitable alkyl cellulose, to vaporizethe water, and to insolubilize the resin.

In contrast to the procedure required with the composition described inour copending application, the dyed fabric can be dried by passagedirectly over conventional drying equipment such as steam-heated dryingcans maintained at a temperature in the range of 210 to 250 F. orthrough a drying oven maintained at a temperature on the order of 250 F.No migration or flocculation of the pigment takes place during suchdrying,

and the dried fabric presents an evenly dyed appearance. Quick heatingof the dyed fabric to initially precipitate the heat-precipitable alkylcellulose prior to any appreciable vaporization of the water is notnecessary. 7

Similarly, insolubilization of the resin can be effected under much lesssevere conditions than those required in the process of our copendingapplication. A satisfactorily wash-fast product can be obtained byfurther passage of the dried fabric over the drying cans or through thedrying oven utilized in the drying step. We have found that conditionsno more severe than on the order of three minutes at 250 F. arenecessary for effective curing of the resin. The dried fabric can, ofcourse, be cured at higher temperatures, in which case the time requiredto complete the cure is materially less. I I

Only'a relatively small amount of the watersoluble heat-precipitablealkyl cellulose as compared to the amount generally included in thecomposition of our copending application is required to produce theresults obtained with the present compositiom. Advantageously, theconcentration of the 'alkyl cellulose ranges from about 0.05 to about0.15% by weight although satisfactory control of migration of thepigment on drying can be obtained in some cases with concentrations'aslow as 0.02% by weight. At concentrationsbelow 0.02%, however, thefinished fabric begins-to evidence undesirable pigment migration.mHighe'r concentrations of alkyl cellulose can also be used; atconcentrations in excess of about 0.25% byweight, however, a gradualdecrease in the degreeof low-temperature fastness of the dried fabricbecomes apparent. Moreover, there is no particular advantage in usingmuch higher concentrations.

The effective controlof migration and flocculation of thepigment'obtained upon drying of a fabric dyed with the present low-alkylcellulose composition appears to be due to the presence of thehydrophilic glycoside. Although th heatprecipitation characteristic ofthealkyl cellulose appears to'play a part in the control of themigration and flocculation obtained, it alone is not responsible forsuch results; for, as already indicated, no effective control of suchmigration and flocculation is obtained upon drying of a fabric dyed witha pigmented aqueous dispersion containing such a water-soluble alkylcellulose alone in the concentrations preferably employed in carryingout the present process. On the other hand, a fabric dyed with anaqueous pigment dispersion containing the hydrophilic glycoside aloneexhibits migration and flocculation of the pigment. Theheat-precipitable alkyl cellulose and thehydrophilic'glycosideapparently coact of cooperate in some manner, thenature of which is not fully understood; for both are necessary for theproduction of a level, even dyeing, and only with both is effectivecontrol of pigment migration. possible. A mixture ofnonheat-precipitable methyl cellulose ether and nonheat-precipitablehydroxyethyl cellulose ether, for example, does not serve the purpose;again, a mixture of nonheat-precipitable sodium carboxymethyl celluloseether and nonheat-precipitable hydroxyethyl cellulose ether does notprevent migration of the pigment on drying.

The less severe conditions required for the curing of the resinsimilarly appear to be due to the presence of the hydrophilic glycoside.Why

the hydrophilic glycoside exerts this desirable effeet on the curing ofthe resin is not known. That it does is clear, however; for, in itsabsence, as in the alkyl cellulose system described in our copendingapplication, a higher temperature or a longen time or both are necessaryto obtain the same comparative cure of the resin. It may be that thehydrophilic glycoside and the resin react in some manner; for, asthe-amount of hydrophilic glycoside such as water-solublenonheat-precipitable hydroxyethyl cellulose ether is increased, theamount of resin remaining constant, the resulting dyed fabric exhibits amarked increase in washfastness.

An important feature of our invention is that, in those cases where adyed fabric having a certain amount of initial crispness or stiffness isdesired, the separate starch-finishing. treatment customarily employedfor this purpose can be eliminated. In imparting such a crisp feel to afabric in accordance with the present procedure, we treat the fabric tobe dyed with a composition containing an amount of hydrophilic glycosidesufiicient to provide the desired'crispness in the finished fabric andsubject the wet dyed fabric to heat sufficient to dry the fabric and toset the resin. We have had particular success in this respect withpad-dyeing compositions containing the higher viscositynonheat-precipitable cellulose ethers such as those hydroxyethylcellulose ethers having a viscosity in excess of about 1,000 centipoises(viscosity of a 2% aqueous solution at.20 C.) Moreover, even though thiscrispness tendsto disappear during subsequent laundering of the fabric,the color value of the dyed fabric remains substantially unimpaired.

The proportion of the hydrophilic glycoside in the present compositionmay vary widely, the amount used depending in part on the particularhydrophilic glycoside employed, the viscosity desired in the paddingliquor, the type of fabric being-dyed and the nature of the finishedproduct. Suflicient hydrophilic glycoside should be used, of course, toinsure the desiredcon-trol of pigment migration and flocculation ondrying. Generally, however, a concentration within the range of about0.25 to 3% by weight is suflicient to produce the desired results.Unless an unusually stifl hand is desired in the finished fabric, noparticular advantage is gained in using greater amounts. Where it isdesired to produce a fabric having a crisp hand, an amount ofhydrophilic glycoside on the order of at least 1% by weight is generallynecessary to produce a satisfactory result.

The color value of a fabric dyedin accordance with the present inventionis substantially indes pendent of the viscosity type of alkyl cellulose.

With the alkyl cellulose system of our copending application, there is agradual decrease in the color value as the viscosity type of the alkylcellulose is increased. In the present composition, however, anyviscosity type of alkyl cellulose can be used, care only being takenthat a smooth homogeneous solution is obtained with the higher viscositytypes. For convenience, however, we prefer to use the low and mediumviscosity types, e. g., in the case of methyl cellulose, those typeshaving a viscosity substantially lower than 1,500 centipoises (averageviscosity of a 2% aqueous solution at 20 C.)

Where the hydrophilic glycoslde comprises a nonheat precipitablecellulose ether, the viscosity type does not appear to have anysignificant efiect on the control of pigmentmigration and flocculationobtained with the present composition or on the color value of a fabricdyed therewith. A greater degree of crispness or stiffness in thefinished fabric is obtained, however, as the viscosity of such acellulose ether is increased particularly when such cellulose ethercomprises a hydroxyalkyl cellulose ether; and, as already indicated,

where such a characteristic is desired in the final product, we preferto utilize the higher viscosity types of hydroxyethyl cellulose ether inour present composition. Especially good results. have been obtainedwith a water-soluble nonheat-precipitable hydoxyethyl cellulose etherhaving a viscosity in excess of 1,000 centipoises.

The concentration range Of the water-soluble thermosetting resin depends,on a number of factors such as the particular resin employed, the typeof fabric being dyed, the depth of shade, and the degree ofwash-fastness desired. In general, the lower limit ofconcentrationdepends on the minimum ratio of resin to pigment required to give thewash-fastness desired in the finished fabric. The upper limit ofconcentration depends on the maximum stiiiness permissible in thefinished fabric. Concentrations as low as on the order of a few tenthsof a per cent 7g tenter maintained at a temperature of 350 to by weightcan be used where only cheap dress goods of moderate wash-fastnes arebeing produced, for example. Generally, however, the preferred range ofresin concentration is on the order of 0.5 to 10% by weight, theparticular concentration employed depending largely on the nature of theparticular application.

A special advantage of. the present system is that the dyed fabric canbe printed with a I vat or an azo color immediately after being dyed.

Dryingon the steam cans'or in the low-temperature oven-imparts a degreeor wash-fastness adequate to withstand the subsequent acidorsteam-aging. In addition, where acid-aging is used, the resin maybesufilciently cured so that the customary curing step may be dispensedwith.

Various types of fabrics can be dyed by means of our improvedcomposition, andthe' application of our invention is not limited to thedyeing of any particular fabric. Excellent control of migration and.flocculation of the pigment with theproduction of an evenly dyed fabricis obtained equally well whether the fabric being dyed is composed ofnatural fibers such as cotton, flax, wool and hair fibers, of syntheticfibers such as regenerated cellulose, cellulose acetate, polyamide,protein polymer, vinyl polymer, andthe like fibers, of inorganic fiberssuch as glass, mineral, or metal fibers, or-of mixtures of such fibers.Furthermore, the application of our process is not limited to the usualtypes Of woven or knitted fabrics but may also be used to dye pilefabrics,

paper, or fabrics made by processes such as combing, matting, orfelting, e. g., a fabric composed of loosely meshed cotton fibers bondedtogether by the localized application of a resin. The present invention,moreovenis equally applicable whether a light or a heavy fabric is beingdyed. (The term fabric as used in the claims includes all these varioustypes of materials as well as yarns, to the dyeing of which ourinvention is also applicable.)

The following examples are typical illustrations of the application ofour invention:

Example 1 3% aqueous solution of high-viscosity water-soluble nonheatprecipitable hydroxyethyl cellulose ether 50.0 5% aqueous solution of 25cps. water-soluble heat-precipitablemethyl cellulose.-- 1.6 Water 47.2aqueous solution of water-soluble polyhydric alcohol modifiedmelamine-formaldehyde resin 0.8 25% water-extendible dispersion of ironoxide red 0.4

A fabric, "for example, printed cotton dress goods, is padded with thisliquor on a two-roll padder. The padded fabric is passed over a seriesof steam-heated cans to precipitate the methyl cellulose and to dry thefabric. Finally, the resin is cured and the fabric is finished byexposing the dried fabric for one minute in a housed 9 380 F. Thiscombination dyeing and finishing operation produces an evenly dyedfabric having a relatively stifi hand and good crock-fastness. Thewash-fastness of the finished fabric is satisfactory for cheap dressgoods.

I Example 2 A padding liquor containing 0.5% of nonheatprecipitablecarboxymethyl cellulose ether, 0.1% of heat-precipitable methylcellulose, 0.5% of resin, and 0.25% of pigment is prepared by mixingtogether the following ingredients:

5% aqueous solution of low-viscosity water-soluble nonheat-precipitableso- A fabric, for example, cotton dress goods, is pad-dyed with thisliquor. The wet dyed fabric is passed directly through a gas-firedhot-flue oven maintained at a temperature of about 350 F. to precipitatethe methyl cellulose and to cure the resin. This procedure gives anevenly dyed fabric with considerable hand and is suitable for cheapdress goods.

Example 3 A pad liquor containing 1.0% of nonheatprecipitablehydroxyethyl cellulose ether, 0.1% of heat-precipitable ethyl cellulose,0.5% of resin and 0.5% of pigment is prepared from the followingingredients:

3% aqueous solution of high-viscosity water-soluble nonheat-precipitablehydroxyethyl cellulose ether 33.33 10% aqueous solution ofmedium-viscosity water-soluble heat-precipitable ethyl cellulose 1 1.00Water 60.92 50 aqueous solution of water-soluble polyhydricalcohol-modified melamine-formaldehyde resin--. 1.00 20%water-extendible dispersion of phthalocyanine blue 1.25 10%water-extendible dispersion of a vat blue (Color Index No. 1113) 2.50

A fabric, for example, cotton dress goods, is pad-dyed with this liquorand is then dried by passage over steam-heated drying cans The driedfabric is printed with stabilized azo colors or with a combination ofsuch colors and pigment colors and is again dIiedonsteam-heateddrying'cans. The printed fabric is next passed through an acid ager todevelop the printed colors and to cure the resin and is then soaped andwashed in the manner customary for stabilized azo prints. Finally, thefabric is finished by exposure for one minute in a housed tentermaintained at 350 F. An evenly dyed fabric with a crisp hand isobtained.

' Example 4 A' pad liquor containing 0.5% of nonheat-precipitablehydroxyethyl cellulose ether, 0.1% of 1 Water heat-precipitable methylcellulose, 0.5% of resin and 1.25% of pigment is prepared by mixingtogether the following ingredients:

10% aqueous solution of low-viscosity'watersoluble nonheat-precipitablehydroxyethyl cellulose ether 5.0 10% aqueous solution oflow-viscosity-watersoluble heat-precipitable methyl cellulose 1.0 Water78.5 50% aqueous solution of water-soluble polyhydric alcohol-modifiedmelamine-formaldehyde resin 1.0 50 aqueous solution of diammoniumhydrogen phosphate 2.0 10 water-extendible dispersion of .a vat blue(Color Index No. 1113) 12.5

A fabric, for example, a rayon sports goods is padded with the above padliquor on a threeroll padder. The wet dyed fabric is then passed over aseries of steam-heated drying cans, and finally for one minute through acuring oven maintained at 300 F. An evenly dyed fabric with asatisfactory fastness to laundering and crocking is obtained.

Example 5 A padding liquor containing 0.5% of locust bean gum, 0.1% ofheat-precipitable methyl cellulose, 0.5% of resin and 0.2% of pigment isprepared by mixing together the following ingredients:

2% aqueous solution of locust bean gum 25 10% aqueous solution oflow-viscosity watersoluble heat-precipitable methyl cellulose 1 69 50%aqueous solution of water-soluble polyhydllc alcohol-modifiedmelamine-formaldehyde res 1 5%aqueous solution of diammonium hydrogenphosphate I 2 10% water-extendible dispersion of a pigment prepared bycoupling para-nitro-orthotoluidine with the ortho-toluidide ofbetaoxy-naphthoic acid 2 A fabric, for example, cotton dress goods, ispadded with the above padding liquor on a tworoll padder. The wet dyedfabric is passed directly to an oven maintained at 275 F. to dry thefabric and to cure the resin. This procedure gives an evenly dyed fabricwith a hand suitable for cheap dress goods.

. Example 6 A padding liquor containing 1.0% of guar flour, 0.1% ofheat-precipitable methyl cellulose, 0.25% of resin and 0.25% of pigmentis prepared from the following ingredients:

2% aqueous solution of guar flour 50.00 10% aqueous solution oflow-viscosity water-soluble heat-precipitable methyl cel- A fabric. forexampl cotton dress goods, is padded with this liquor on a three-rollpadder. The padded fabric is dried and the resin is cured by passageover a series of high-pressure steamheated drying cans. This proceduregives an evenly dyed fabric with a crisp hand and a fastness tolaundering and cracking satisfactory for cheap dress goods.

. Example 7 A. padding liquor containing 0.75% of guar flour, 0.25 ofnonheat-precipitable hydroxyethyl cellulose ether, 0.1% ofheat-precipitable methyl cellulose, 1.0% of resin and 0.5% of pigment isprepared from the following ingredients:

2% aqueous solution of guar flour 37.5 10% aqueous solution ofmedium-viscositywater-soluble nonheat precipitable hy- A fabric, forexample, cotton dress goods, is padded with this liquor on a two-rollpadder. The wet fabric is dried on steam-heated drying cans and isfinished by passage through a housed tenter maintained at about 300 F.This procedure gives an evenly dyed fabric with a crisp hand and withgood fastness to laundering and crocking.

Example 8 A padding liquor containing 1.0% of nonheatprecipitable methylcellulose ether, 0.1% of heatprecipitable methyl cellulose, 0.5% ofresin and 1.25% of pigment is prepared by mixing together the followingingredients:

10% aqueous solution of water-soluble nonheat-precipitable methylcellulose d ether 10% aqueous solution of low-viscosity water-solubleheat-precipitable methyl cellulos 1.00 Water 79.75 50% aqueous solutionof water-soluble polyhydric alcohol-modified melamineformaldehyde resin.1.00 5% aqueous solution of diammonium hydrogen phosphate 2.00 20%water-extendible dispersion of copper phthalocyanine green. 6.25

A fabric, for example, rayon sports goods, is padded with the aboveliquor and the wet dyed fabric is dried and the resin is cured bypassage soluble nonheat-precipitable 1, in which the hydrophilicsubstance comprises.

. Our pigment-dyeing composition. as already indicated, can beconveniently applied to a fabric by a padding operation. Other methodsof applying the pigment-dyeing composition can also be employed,however; for example. the dyeing composition can be applied to a fabricby forming a thin film thereof on a roll-coating machine and thentransferring. the film to the fabric.

We claim:

1. A dyeing composition comprising a dispersion of a water-insolublepigment in an aqueous solution of a water-soluble thermosetting resin, awater-soluble heat-precipitable alkyl cellulose,

and a hydrophilic substance selected from the group consisting ofwater-soluble nonheat-precipitable cellulose ethers and mannogalactanflours containing a major proportion of mannogalactan, the proportion ofthe thermosetting resin being between 0.5 and 10% by weight based ontotal composition, that of the heat-precipitable alkyl cellulose between0.02 and 0.25% by weight based on total composition, and that of thehydrophilic substance between 0.25 and 3% by weight based on totalcomposition.

2. The dyeing composition as claimed in claim 1, in which thehydrophilic substance comprises a water-soluble nonheat-precipitablehydroxyalkyl cellulose ether. p 3. The dyeing composition as claimed inclaim 2, in which the water-soluble nonheat-precipitable hydroxyalkylcellulose ether comprises a waterhydroxyethyl cellulose ether. v

4. The dyeing composition as claimed in claim locust bean gum.

5. The dyeing composition as claimed in cla 1, in which the hydrophilicsubstance comprises guar flour.

6. The method of evenly pigment-dyeing a fabric without migration andflocculation of the pigment on drying, which comprises applying to thefabric a dispersion of a water-insoluble pigment in an aqueous solutionof a water-soluble thermosetting resin, a water solubleheat-precipitable alkyl cellulose, and a hydrophilic substance selectedfrom the group consisting of water-soluble nonheat-precipitablecellulose ethers and mannogalactan flours containing a major proportionof mannogalactan, the proportion of the thermosetting -resin beingbetween 0.5 and 10% by weight based on total dispersion composition,that of the heat-precipitable alkyl cellulose between 0.02 and 0.25% byweight based on total dispersion composition, and that of thehydrophilic substance between 0.25 and 3% by weight based on totaldispersion composition. and thereafter heating the fabric to dry it andto hi solubilize the resin.

'7. The method of evenly pigment-dyeing a fabric as claimed in claim 6,in which-the hydrophilic substance comprises a water-solublenonheat-precipitable hydroxyalkyl cellulose ether.

8. The method of evenly pigment-dyeing a fabric as claimed in claim 7,inwhich the watersoluble nonheat-precipitable hydroxyalkyl celluthroughan oven maintained at 300 F. An evenly dyed fabric with good fastness tolaundering and crocking and having a full and soft hand is o tained.

lose ether comprises a water-soluble nonheatprecipitable hydroxyethylcellulose ether.

9. The method of evenly pigment-dyeing 9. fabric as claimed in claim 6,in which thehydrophilic substance comprises locust bean gum.

10. The method of evenly pigment-dyeing a 13 14 fabric as claimed inclaim 8, in which the hydro- UNITED STATES PATENTS phiiic substancecomprises guar flour. Number Name Date NORMAN CASSEL- 2,245,491 Mengeret a1. June 10, 1941 ALFRED 5 2,270,130 Bass et a1. Jan. 13, 19422,275,991 Powers et a1. MarJlO, 1942 REFERENCES CITED 2,336,484Klinkenstein et a1. Dec. 14, 1943 The following references are of recordin the 2,370,517 Bass et a1 Feb. 27, 1945 file h Patent: 2,378,322Peterson June 12, 1945

1. A DYEING COMPOSITION COMPRISING A DISPERSION OF A WATER-INSOLUBLEPIGMENT IN AN AQUEOUS SOLUTION OF A WATER-SOLUBLE THERMOSETTING RESIN, AWATER-SOLUBLE HEAT-PRECIPITABLE ALKYL CELLULOSE, AND A HYDROPHILICSUBSTANCE SELECTED FROM THE GROUP CONSISTING OF WATER-SOLUBLENONHEAT-PRECIPITABLE CELLULOSE ETHERS AND MANNOGALACTAN FLOURSCONTAINING A MAJOR PROPORTION OF MANNOGALACTAN, THE PROPORTION OF THETHERMOSETTING RESIN BEING BETWEEN 0.5 AND 10% BY WEIGHT BASED ON TOTALCOMPOSITION, THAT OF THE HEAT-PRECIPITABLE ALKYL CELLULOSE BETWEEN 0.02AND 0.25% BY WEIGHT BASED ON TOTAL COMPOSITION, AND THAT OF THEHYDROPHILIC SUBSTANCE BETWEEN 0.25 AND 3% BY WEIGHT BASED ON TOTALCOMPOSITION.